Search Documents

By Howard W. Wainwright

The Bureau of Mines is engaged in a research program on the characterization of tars produced by low-temperature carbonization of coal and their economical upgrading to more valuable materials, Throughout the years, hydrogenation has played an important role in the treatment of these tars, mainly as a means of converting the whole crude tar or selected fractions to motor fuels; diesel oil, lubricating oil, or various solvents. In some instances, production of specialty chemicals has been the objective. The purpose of this report is to summarize, without critical review, the information of the past 25 years on the hydrogenation of low-temperature tars and related substances as presented in the literature or its English translation. Published articles and patents not abstracted in the main body of this report are included in a bibliography at the end. HYDROGENATION REACTIONS The hydrogenation of tar follows three general types of reactions; 1. The removal of oxygen, sulfur, and nitrogen in the tar to form water, hydrogen sulfide, and ammonia, respectively: [ ]

Jan 1, 1961

By Robert H. Merrill

Measurement of the deformation of a borehole in rock subjected to a change in applied stress can be used to calculate the magnitude and direction of the applied stress, provided a satisfactory deformation-applied stress relationship exists , In this investigation by the Bureau of Mines the deformation of a bore- hole in a rock model subjected to a known applied stress was compared with the theoretical deformation of a hole in an elastic, isotropic plate and was found to be in good agreement. Hence, this relationship can be used to calculate the applied stress on a borehole from borehole deformation measurements.

Jan 1, 1961

By K. K. Kershner

Sulfide ore concentrates containing cobalt, nickel, copper, lead, and iron were salt roasted and leached on a laboratory scale. More than 95 percent of the cobalt, nickel, and copper was recovered. Heating patterns for salt roasting different concentrates were established. More cobalt, nickel, and copper were recovered from a bulk concentrate composed of a mixture of copper concentrate and iron concentrate. This mixture corresponded roughly with the mixture of these materials in stockpiles in southeastern Missouri. A temperature range of 375° to 400° C. was best for salt roasting. Metal chlorides were leached at a pH of 1 from chloridized charges of concentrates, Although the amounts of cobalt, nickel, and copper extracted were high, the amount of iron dissolved simultaneously interfered with subsequent separation and recovery of these metals. The amount of dissolved iron was reduced substantially by steam treating chloridized charges of bulk concentrate at 300° C. In this way, the ratios of cobalt, nickel, and copper to iron in leach liquors permitted satisfactory separation and recovery of these metals. INTRODUCTION The Federal Bureau of Mines is experimenting with chloridizing reactions.4 5 6 7/ Salt roasting of sulfide ores and concentrates, or their calcines, to form metal chlorides has certain advantages. Chlorides of

Jan 1, 1961

By H. F. Yancey

Traditionally the Pacific Northwest has relied on hydroelectric power, which has been both abundant and cheap. However, comparatively few hydroelectric sites capable of providing low-cost power remain, therefore the need for supplemental thermal generation, perhaps within the next decade, is generally recognized. Based on the present cost and availability of competing fuels, coal seems to be the logical choice for projected thermal power plants. Power companies and public utilities have become interested in establishing reserves of coal for future use. One deposit explored in 1958-59 lies in southern Thurston and northern Lewis Counties, Wash., near Centralia. Drilling, totaling 22,700 feet, proved the existence of 70 million tons of strippable coal--an ample reserve for the projected power plant. The coal, like most others and particularly those of Washington and Oregon, when mined in full seam section by mechanical methods, would require cleaning to make it suitable for use. The amount and nature of the impurities in this coal dictated a thorough investigation of its cleaning characteristics to establish economic factors and to insure proper preparation-plant design. Therefore, arrangements were made through a cooperative agreement to conduct such work at the Seattle Coal Research Laboratory of the Bureau of Mines. This report describes that investigation. The results are of interest primarily in connection with the utilization of this particular deposit, but some of the information developed is applicable to other deposits of low-rank coals in the West, because the impurities in these coals differ greatly in behavior from those generally associated with the higher rank coals of the Appalachian field.

Jan 1, 1961

By Lowell Stroud

Since 1929, the Helium Activity of the Bureau of Mines has operated a helium-extraction plant at Amarillo, Tex. The natural gas that supplies this plant is obtained from the Cliffside geologic structure 12 miles to the northwest and over the years, has become known simply as "Cliffside gas," There is need for published data on the low-temperature phase equilibria of helium-bearing natural gases. To date, little information has been published on the equilibrium phase compositions, solution of helium in condensed natural gas, condensation characteristics, or equilibrium vaporization coefficients for methane, nitrogen, and helium in helium-containing systems. A windowed phase equilibrium apparatus (8)6 was used to obtain 105 equilibrium samples, representing 35 experimental conditions of condensed Cliffside gas at pressures of 100, 200, 300, 400, and 500 p.s.i.a. and temperatures from 0° to -270° F. Data on equilibrium vapor-liquid composition for Cliffside gas are presented in both tabular and graphic form and are discussed in detail to show their relationship to certain criteria that must be met to effect an efficient separation of helium from natural gas by means of low-temperature processes. Facts about condensation characteristics and solution of helium in the liquid phases are included, The important relationship of these two factors in decreasing the percentage of total helium lost by solution in the liquid phase is discussed.

Jan 1, 1961

By A. L. Engel

This report is a compilation of preliminary and, in some cases, more extensive concentration experiments by the Federal Bureau of Mines on low-and medium-grade fluorspar ores from three localities in Nevada and one in California. The work was done on samples obtained from Shoshone mine, Nye County, Valery mine, Pershing County, and the Broken Hills mine, Mineral County, all in Nevada, and Dirty Weather mine, Inyo County, Calif. These investigations were made to aid in the development of domestic fluorspar resources, in line with the Bureau's long-established program of conservation of mineral resources. The treatment methods employed in the experimental work described included simulated or "heavy-liquid" gravity concentration of coarse minerals and comparatively fine-grained minerals, and flotation concentration of finely-ground minerals. These methods were attempted in order to beneficiate the ores and produce concentrates which could be marketed readily, with as high a recovery rate as possible, while using simple treatment methods suitable for small-scale operation.

Jan 1, 1961

By D. P. R. Smyth

The limestone reef reservoir at Swan Hills consists essentially of a "buildup" of successively smaller atoll-like layers. Precipitation of calcium carbonate within the lagoonal area of each layer essentially kept pace with growth of the outer organic lattice. Within the reef mass, six de-positional environments characterized by specific suites of fossils (or fossil fragments) and associated limestone textures are recognized as follows: ( 1) Aerated moderately agitated water of normal marine salinity (widespread shelf or submerged reef-built platform). Thamnopora-type corals, Amphipora, "pancake" stroma-toporoids, crinoids, articulate bra-chiopods, rare rugose cup corals, and ostracods occurs in light gray-buff skeletal microgranular limestone of low permeability. (2) Semi-stagnant quiet water of normal marine salinity (leeward side of reef). Crinoids, articulate brachio-pods, rare thamnopora-type corals, Amphipora, pancake and bulbous stromatoporoids, rugose cup corals, ostracods and gastropods occur in impermeable dark brown argillaceous skeletal calcilutite with thin black bituminous shale beds and rare dark chert nodules.

Jan 1, 1961

By Kenneth G. Broadhead

The objective of this rare-earth oxalate study by the Bureau of Mines was to determine systematically by radiochemical techniques what effects, if any, could be attributed to the several variables--temperature, digestion time, acid concentration, rare-earth concentration, oxalic acid concentration, stirring, and the presence of other rare-earth ions. A Latin Square experimental design was used to evaluate statistically some of the variables. Precipitation losses ranged from near zero to about 7 percent, and mineral acid and rare-earth concentration were the predominant factors affecting completeness of precipitation. Quantitative oxalate precipitation of the rare-earth elements was achieved by controlling the experimental conditions as follows: (1) Maintaining rare-earth concentrations above 0.01M; (2) stirring the mixture several minutes after precipitation; (3) using an adequate (two to five-fold) excess of oxalic acid; (4) precipitating at room or iced temperature and digesting for at least 1 hour; (5) avoiding an excess of mineral acid and, if possible, maintaining the pH above 2.0; and (6) avoiding excess complexing agents such as EDTA (ethylenediaminetetraacetic acid). In the past 20 years research aimed at developing more efficient separation and purification techniques applicable to the rare-earth elements and yttrium has been extensive. Common to most of these procedures has been the use of oxalic acid to precipitate this group of elements selectively. However, this particular use of oxalic acid has a much earlier origin; its application in precipitating yttrium was first reported by Mosander (8)4 in 1843. Despite long and popular employment of this technique, only limited and somewhat conflicting data are available regarding the many factors affecting the degree of rare-earth oxalate precipitations.

Jan 1, 1961

By D. A. Wilson

Several promising systems for selectively oxidizing the iron in an iron-tin alloy commonly called "hardhead" were investigated in a research project conducted to devise a method for recovering tin from this troublesome alloy. A satisfactory oxidation method was developed and tested successfully on melts of 2,000 grams. Molten hardhead (near 1,080° C.) was blown with air to oxidize iron and leave tin in the reduced state. Recovery of available tin was 96 to 98 percent. Tin products contained 2 to 0.1 percent iron which was reduced to 0.06 percent by filtration at 250° C. Iron oxide formed during oxidation was absorbed by a fluid flux cover composed of 43 percent silica, 17 percent burned limestone, and 40 percent fused borax. Less successful but nevertheless promising results were obtained with mixtures of steam and hydrogen which were sufficiently selective at temperatures between 600° and 950° C. but did not result in complete oxidation of iron. Carbon dioxide-carbon monoxide mixtures also oxidized iron selectively but incompletely. Both stern and carbon dioxide systems produced sufficiently encouraging results to additional research on these systems.

Jan 1, 1961

By C. R. Fahnestock

One of the major problems for us in the earthmoving industry is the analysis of materials under the ground surface. Countless engineering and construction jobs would be simplified if there were an inexpensive and fast way to obtain information on problems such as: Depth and solidith of bedrock? Nature of the materials between bedrock and the surface? Adequate foundation for bridges and drainage structures? Location of supplies of materials to be used in construction? Investigation of tunnel sites? Characteristics of swampy areas and investigation of existing and potential slide areas? These questions are of paramount interest to highway contractors as they bid jobs and plan, equipment spreads to handle them at optimum efficiency. Such information also is invaluable to engineers in the design and construction of bridges, buildings, railroads, canals, and tunnels.

Jan 1, 1961

By J. B. Gayle

Although heated circuits frequently have been employed in the conditioning stases of certain flotation processes, particularly the flotation of fluorite, the control of temperature is not generally considered economically feasible for the flotation of coal. This viewpoint, although widely held, can neither be substantiated nor refuted by reference to published data. Some evidence is available, however, that temperature is an important variable in the floatability of coal as well as other minerals. For example, Gayle and Swelley4 found that contact angles for coal and related substances were definitely dependent on temperature. Bailey and Whalan5 showed that changes in pulp temperature may exert a pronounced influence on recoveries of coal in batch flotation tests. The present laboratory-scale investigation was undertaken to obtain information about the effects of changes in pulp temperature on coal flotation recovery and also on the selectivity of separation possible using different reagents. The results indicated that flotation recoveries were markedly affected by temperature variations when certain reagents, particularly simple aliphatic alcohols, were used. For other reagents, particularly kerosine, flotation recoveries were substantially independent of variations in pulp temperature. Release-analysis results indicated that temperature variations did not greatly affect the selectivity of separation possible with the reagents tested.

Jan 1, 1961

By R. W. Guard

ALTHOUGH etching techniques have been developed for revealing dislocation sites in several metals and ionic crystals,h t is valuable to extend the technique to new metals. An etch pit method for nickel has been developed on the basis some suggestions of Dr. John R. Cuthill of the National Bureau of Standards who had observed etch pits in creep specimens of nickel. The etchant used was proposed first by wensch2 for revealing grain size in nickel. The present paper describes the evidence that the technique can be used to reveal dislocations and gives the conditions under which etching can be carried out. The specimens examined were vacuum melted high-purity Ni (99.985 pct Ni) and commercial "A" nickel (99.8 pct Ni). Both materials contained greater than 0.008 pet C and had been annealed in nitrogen or dry hydrogen at 1100o to 1200°C. This gave a grain size of 1.5 mm in the high-purity nickel and 0.050 mm in "A" nickel. Tensile specimens (0.254 in. diam) were deformed from 0.25 to 10 pct at room temperature and then heated for 1/2 hr at different temperatures from 400" to 900°C. The specimens were sectioned longitudinally then polished electrolytically in 60 pct H2SO4 and etched in 35 pct H3PO4 solution at 0.2 to 0.4 v for 30 sec to 3 min. The best method for setting the proper voltage for etching is to increase the voltage until gas bubbles are evolved vigorously from the specimen and then cut it back by 10 pct. It is necessary to heat the specimen above 500°C after deformation in order that etch pits will be formed. This "decoration" treatment permits carbon to segregate to the dislocation rendering them sensitive to etching. It was demonstrated that carbon was the decorating impurity by decarburizing some specimens in wet H2 at 1200°C. The susceptibility to etch pitting was lost following this treatment but could be restored by carburizing in contact with graphite. Some rearrangement of the dislocations in the as-deformed structure occurs on heating at 500oC and above so that the technique can not be used to study the nature of dislocation patterns in deformed specimens. Extended etching does not change the number of pits although the background becomes rough and the pits quite large. The polycrystalline specimens with various strains were examined after annealing at different temperatures. Typical patterns are shown in Figs. 1 and 2. In the unstrained specimen, Fig. 1, the density of pits is 2.5 X 10' per sq cm. All grains show pits regardless of their orientation although there is a

Jan 1, 1961

By P. G. Clites

A laboratory furnace was developed by the Federal Bureau of Mines for use in studying the interrelationships among variables associated with skull melting and casting high-temperature metals. Although additional work is necessary to determine the extent to which the information obtained by using this furnace can be extrapolated to larger furnaces of the same type, many casting characteristics of metals and alloys can be determined on equipment of this size. This furnace is a laboratory-size, consumable-electrode, skull-casting furnace equipped with a water-cooled copper ladle. The ladle, which is a tilt-pour or over-the-lip type, has a volume of approximately 30 cubic inches and provides up to 20 cubic inches of molten metal for castings. Castings of various reactive and refractory metals, including zirconium, titanium, hafnium, columbium, molybdenum, tantalum, and tungsten, have been produced. In addition, castings of iron, chromium, and copper have been made. The simplicity and versatility of the apparatus would make it useful to metallurgical laboratories preparing cast specimens.

Jan 1, 1961

By R. C. Tait

The gold at Giant Yellowknife is intimately associated with a complex mixture of sulphides, including pyrite, arsenopyrite, stibnite, and a wide variety of antimony sulpho-salts. Direct cyanidation has never been feasible. Recovery is almost entirely dependent upon flotation, roasting of flotation concentrate, and cyanidation of calcine. In November 1958, an Edwards-type roaster and an early prototype, two stage Fluosolids roaster, were replaced by a large two-stage Fluosolids roaster of improved design. The new roaster was started at "safe" medium temperatures, but early in 1959, temperatures in both stages were gradually and deliberately lowered to determine whether continuous autogenous roasting could be maintained under exacting low temperature conditions necessary for good extraction. Operation is smooth and continuous with first and second stage temperatures controlled at 925° and 875°F respectively. Plant cyanide ex-traction compares very favourably with extraction from low

Jan 1, 1961

By H. U. Ross

ROASTING is usually thought of as a process in which finely crushed or ground ore is heated with air in a suitable furnace in which the ore is rabbled or agitated in such a way as to insure complete reaction between the oxygen of the air and the oxidisable constituents of the ore. Roasting in this sense is used only to a very limited extent in the iron and steel industry. This is because, in most iron ore deposits mined today, the ore is of a type that does not require roasting. Where this process is used, it is usually because of some special circumstance, such as a peculiar economic condition, that warrants it. If roasting is looked upon in the broader sense as a gas-solid chemical reaction carried out at an elevated temperature in which both gaseous and solid products are formed, then the process is used in the iron and steel industry to a greater extent

Jan 1, 1961

By A. L. Engel

This report describes results of laboratory-scale experimental treatment of nine ores containing gold and silver, including samples of products of previous plant treatment, from ore deposits in California and Nevada. The samples treated were taken by engineers of the Bureau of Mines during investigations of these ore deposits. The information reported is of interest for development of the mining districts represented or in future Investigations of similar ores from other sources. The treatment methods were as simple as possible. More complicated treatments were tried when required, The applicability of the methods and their limitations in treating the ores are shown by the data in this report. The following treatment methods were employed in the experiments described: Screen analyses were made to determine distribution of values in various screened-sized portions of crushed ore, or to determine optimum size to which a particular ore should be crushed or ground to liberate values, and some-times to determine residual values in various-sized portions of treated material.

Jan 1, 1961

By E. R. Palowitch

A centrifugal float-and-sink test procedure has been developed by the Bureau of Mines to reduce the time for the gravimetric separation of coals finer than l4-mesh from as long as 24 hours to less than 1 hour. Comparative tests indicated that centrifuging a minus 14-mesh Pittsburgh-bed coal for 20 minutes at 1,500 revolutions per minute produced results that compared favorably with static float-and-sink test results. Standard deviations of the mean recovery and ash content of the float obtained centrifugally ranged from 1.31 and 0.04 percent, respectively, at 1.30 specific gravity to 0.21 and 0.05 percent, respectively, at 1.60 specific gravity. As in static separations, retreatment of the products separated at low specific gravities was required.

Jan 1, 1961

By T. E. Gray

This report describes the preparation characteristics of the significant coalbeds in Harrison County, W. Va. It is one in a series of Federal Bureau of Mines reports planned to determine coals suitable for the production of metallurgical coke, either as mined or after beneficiation. Over 6.5 million tons of coal was produced in Harrison County, W. Va., in 1958, of which over 3.7 million tons was cleaned mechanically in seven preparation plants. All of the coal cleaned was from the Pittsburgh bed. It has been estimated that more than 1,816 million tons of coal remains in the county in beds 12 inches or more thick. The Pittsburgh and Redstone beds were selected by the Bureau for a study based on current production rates and estimated minable reserves. Sample locations were selected following a study of the literature, conferences with mining engineers and mining company officials in the field, and examination of the available sites. Six samples were collected from the Pittsburgh bed, and three samples came from the Redstone bed, Float-and-sink tests of the samples collected from the Pittsburgh and Redstone beds showed that neither coal could be upgraded to a metallurgical fuel under the standards set up for this study, even after intensive preparation. Finer crushing of the samples moderately increased the yields and slightly reduced both the ash and the sulfur contents in the 1.30-specific-gravity float fractions. Finer crushing slightly decreased the yields in the 1.58-specific-gravity float fractions, whereas it reduced the sulfur content 0.11 percent for the Redstone sample and 0.46 for the Pittsburgh sample.

Jan 1, 1961

By Martin H. Stanczyk

The direct dissolution of a typical zinc sulfide flotation concentrate by elevated temperature and pressure leaching was investigated. The concentrate assayed about 55 percent Zn, 32 percent S, 6 percent Fe, and 1 percent Pb and contained minor quantities of copper and precious metals. The influence of various factors on the dissolution of the zinc in acidic and ammoniacal pulps when using oxygen as the oxidant was determined. The tests revealed that the sphalerite was difficult to oxidize. Complete dissolution of the mineral required vigorous and intimate nixing of the gaseous, liquid, and sold phases. The addition of pyrite or sulfuric acid to water slurries of the concentrate was required to obtain a high zinc extraction when leaching under acidic conditions. The quantity of pyrite and acid used was about 0.125 and 0.25 pound, respectively, per pound of zinc sulfide contained in the leach charge. In tests with acid, about 96 percent of the zinc was extracted from the concentrate in 1 hour at 200° C. when the oxygen partial pressure was 75 pounds per square inch gage or higher. Leaching with a continuous flow of air as the oxidant gave results that were almost as good as those obtained when oxygen was used, In tests with air fed through the autoclave at 320 liters per hour, 95 percent of the zinc was dissolved in 1 hour, Acid leach solutions assaying approximately 58 grams Zn per liter and containing Fe, Ni, Cr, and Cu impurities were produced in the better tests. The leached residue consisted essentially of red iron oxide together with substantially all of the lead and precious metals.

Jan 1, 1961

By R. Greenwood

The advent of the space age and its promise of interplanetary flight has prompted new ideas for propulsion systems that will allow maximum energy with minimum fuel weight. The use of cesium as the source of energy for such rocket flights has been found desirable. Theoretical efficiency of a rocket fuel is measured in terms of specific impulse, defined as the number of pounds of thrust per pound of propellant consumed per second. Specific impulse is usually expressed in seconds (the number of seconds for which one pound of fuel would produce one pound of thrust) although it is really a measure of total energy, not of power. The most sophisticated chemical fuels have a specific impulse of 300 to 400 sec; liquid hydrogen heated by nuclear reactor has a specific impulse of 1000 to 1200 sec. Specific impulses as high as 20,000 sec, however, are theoretically attainable with the ion rocket, in which free cesium ions are accelerated across a voltage drop and ejected at high velocity.' Characteristics of the system have been sketched by Boden.2 The desirable properties of an ion propellant are: 1) low ionization potential, 2) low boiling point, and 3) high atomic weight. Alkali metals best fulfill these requirements, and Table I indicates the superiority of cesium. The use of heavy complex ions such as UCl3 is ruled out by their instability and other disadvantages.' Despite its enormous superiority in specific impulse, the ion rocket is inherently low-powered, capable of very small acceleration. Application of ion propulsion will be limited to large rockets and spaceships on missions requiring powered flight for weeks or months and employing a separate chemical propulsion system for escape from the earth's atmosphere where power requirements are large but of brief duration. For example, Kraemer and Larson3 considered the case of an unmanned 25,000-lb pay-load placed in a 300-mile orbit by chemical rockets, proceeding thence by ion propulsion to the vicinity of Mars, where it would go into orbit once again. Calculations provide for 8500 lb of cesium for such a voyage. The question of whether such quantities of cesium will be readily available to the space program does not appear to have been considered by geologists and mining engineers. Present Production and Uses Literature on industrial applications of cesium is scanty. The metal is used in scintillation counters, photocells, infra-red detection devices, and as a "getter" in low-voltage vacuum tubes. Production is sporadic and total figures are not published, but the annual consumption is measured in pounds rather than in tons. The few pollucite deposits known, small as they are, can easily supply the present limited demand for gram or pound lots of cesium. Until recently the price of cesium was $2 to $4 per gram, but according to Chemical Engineering, cesium salts are now available at $13 to $27.50 per lb. Geochemical Distribution As a large alkali ion, the cesium ion accompanies potassium in geological processes and tends to be concentrated in the latest crystallizing fractions of potassium minerals in much the same manner as rubidium. Most of the cesium in igneous rocks, therefore, is in the micas and potash feldspars of granites, and especially in granitic pegmatites. The cesium content rises markedly in the micas of the late by-drothermal replacement stage in complex pegmatite~.' Typically, cesium is only 0.5 to 0.01 times as abundant as rubidium in potassium minerals. Rb', with a radius of 1.47 A, is close enough in size to K' (1.33 A) so that rubidium forms no minerals of its own. Cs+ is so large (1.67 A) that only small concentrations can be taken up in potassium minerals; when cesium is present in solution in larger concentration it forms the mineral pollucite, Cs3-Na2A17Si17O48.3H2O, which is known only in pegmatites. In the weathering of igneous rocks, cesium is dissolved, carried to the ocean, and apparently in-

Jan 1, 1961